DE2517101C2 - Alkyl N-(O-alkyl-s-aliphato-(thiono)thiolphosphoryl)-imino formates - insecticides and acaricides prepd. by reacting (thiono)thiol-phosphoric acid esteramides with alkyl orthoformates - Google Patents

Abstract

Cpds. of formula (I) (where R = 1-6C alkyl; R1 = 2-6C alkenyl, 2-6C alkynyl, lower alkylthioalkyl or N-alkylcarbamoylmethyl; Alk = 1-6C alkyl; X = O or S) are insecticides (systemic) and acaricides used to control plant parasites, in hygiene and storing og goods. (I) are active against both sucking and grinding insects and have low toxicity to warm-blooded animals. They are applied in classical formulations and have good stability and long duration activity on wood and clay. (I) have better activity than known cpds. where R1 = alkyl e.g. methyl.

Description

RO

in which

R alkyl with 1 to 6,

R 'alkenyl or alkenyl with 2 to 6, lower

Alkyl mercaptoalkyl or N-alkylcarbamoyl-

methyl, means while
Alk represents alkyl of 1 to 6 carbon atoms

and
X is an oxygen or sulfur atom.

are characterized by a superior insecticidal and acaricidal effectiveness.

It was also found that the new N- [O-AI-

alkyl-S-aliphatic lithium-thionophosphoryl-iminoformate of constitution (1) can be obtained if O-alkyl (thiono) ihiolphosphorsäureesteramideder formula

RO X

P-NH ₂

(Π)

R'S

2. Process for the preparation of N- [O-alkyl-S-aliphatic ^ thionojthiolphosphorylj-iminoformic acid L-alkyl esters, characterized in that 25 with ortho-formic acid alkyl esters of the formula

one 0-alkyl (ihiono) thioiphosphoric acid sicramides the formula

RO X

R'S

AlkO — CH-OAIk

OAIk

(III)

P-NH ₂

(Π)

with ortho-formic acid alkyl esters of the formula AlkO —CH-OAIk
OAIk

(IU)

implemented, where in the formulas (II) and (III) R, R ', Alk and X have the meaning given in claim 1.

3. Use of compounds according to Claim I for combating insects and mites.

brings to reaction, where in the formulas (II) and (111) R, R ', Alk and X have the meaning given above.

Surprisingly, the benches according to the invention have N-fO-alkyl-S-aliphatic thionoJthiolphosphoryl] iminoformic acid alkylsians a much better insecticidal, especially systemic and insecticidal acaricidal effect than the previously known N- [0.S-Dime-

ethyl thionothiolphosphoryl] formic acid ethyl ester
■ to an analogous constitution and the same direction of action. The substances according to the invention thus represent a real asset to technology.

If one uses O-methyl-S-ethylmercaptoäthylihiolphosphorsäurediesteramid and ethyl orthoformate as starting materials, the course of the reaction can be represented by the following equation will:

CH ₃ O 0

The present invention relates to new N- [O-alkyl-S-aliphatic thionoJthiolphosphorylJ-iminoamcisensäurealkylester, which have an insecticidal and acaricidal effect and a method for their Manufacturing.

It is already known (see German Offenlegungsschrift 21 16 690) that the N- [O, S-dimethyl-thionolhiolphosphorylj-formic acid ethyl ester (Compound A) possesses insecticidal and acaricidal properties.

It has now been found that the new N- [O-alkyl-S-aliphalic thiono-thiolphosphoryll-iminoamcisene acid alkylesierdcr formula

C ₂ H ₅ O

l \

P-NH ₂ + CH-OC ₂ H ₅

C ₂ H ₅ SC ₂ H ₄ SC ₂ H ₅ O

CH ₃ OO

ll

PN = CH-OC ₂ H ₅

-2 ■ C ₂ H ₅ OH

C ₂ H ₅ S - C2H4S

R'S X

P-N = CH-OAIk RO

(I)

The starting materials to be used are generally clearly defined by the formulas (II) and (III). R. preferably represents straight-chain or branched alkyl with I to 4, R 'represents alkenyl or alkynyl with 2 to 4 t, <s carbon atoms, N-monomethyl or N-monoethylcarbamoylmethyl, Methylmercaptoäthyl- and Äthylmercaptoäthyl-, while Alk is preferably straight-chain or branched alkyl with 1 to 3 carbon

atonicn means.

The O-alkyl (ihiuno) -thiolphosphoric acid sieramides required as starting materials (II) are for the most part known and can be carried out by generally customary methods can be easily produced (see e.g. DIi-AS 12 16 835. NL-OS b9 11 925 and DE-OS 21 35 349). The orlho-amciseoic acid alkyl esters (III) and the methods for their preparation are also already described in the literature.

As examples of O-Alkyi (thiono) -ihiolphosphorsäureesteramide (II) and to be used according to the process Ortho-formic acid alkyl esters (III) are mentioned in detail called:

O-methyl-S-allyl-,

O-ethyl-S-allyl,

O-n-Prcpyl-S-allyl-,

O-iso-propyl-S-allyl-,

O-n-butyl-S-allyl-.

O-sec-butyl-S-allyl-,

O-iso-butyl-S-allyl-,

O-tert-butyl-S-allyl-.

O-methyl-S-propargyl-,

O-ethyl-S-propargyl-,

O-n-propyl-S-propargyl-,

O-iso-propyl-S-propargyl-,

O-n-butyl-S-propargyl-,

O-sec-Bulyl-S-propargyl ·.

O-iso-butyl-S-propargyl-,

O-tert-butyl-S-propargyl-,

O-methyl-S- (N-monomethylcarbamoylmethyl) -

thiolphosphoric diesteramide

and the corresponding thiono analogs. as

the methyl, ethyl, or propylsier

of ortho-formic acid c.

The manufacturing process can be carried out with the use of suitable solvents or diluents be performed. Practically all inert organic solvents can be used as such. For this mainly include aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, gasoline, also alcohols such as ethanol and n-butanol, and also nitriles such as aceto- and propionitrile. In general one works, however, without a solvent. Optionally, in the presence of acidic catalysts, such as z. B. p-toluenesulfonic acid, worked.

The reaction temperature can be varied over a wide range. Generally one works between 100 and 250 ° C; preferably between 140 to 160 ° C.

The reaction is generally carried out under normal pressure.

To carry out, the ortho-formic acid component is generally used in a 10 bis A 20% excess and heated the reaction mixture - usually without a solvent - at the specified temperatures for several hours. the Here too, the mixture is worked up as usual by distilling off the alcohol which forms and Distillation of the reaction solution.

The substances according to the invention are mostly obtained in the form of colorless or pale yellow oils and can easily be distilled without decomposition; therefore they are freed from the last volatile constituents by so-called "flattening", that is, by prolonged heating under reduced pressure to moderately elevated temperatures and cleaned in this way. 7. » the refractive index is used to characterize them.

As already mentioned several times, the N ^ O-alkyl-S-aliphatic orthoJthiolphosphoryl] -

iminoformic acid alkylesicr by excellent

. insecticidal, especially systemic-inseclicidal and acaricidal activity against plant, hygienic and

Pre-rais pests. You have both a

good effect against sucking as well as eating

Insects and mites (acarina). You own at the same time

ίο low toxicity to warm blooded animals; d. H. mostly e: ne 5- to

10 times lower toxicity to warm-blooded animals than the starting products (H).

For this reason, the compounds according to the invention are successfully used as pesticides, mainly used in crop protection.

The sucking insects mainly include aphids (Aphidae) such as the green peach aphid (Myzus persicae), the black bean (Doralis fabae). Oat (Rhopalosiphum padi). Pea (Macrosiphum pisi) and potato mousse (Macrosiphum solanifolii), also the currant gall (Cryptomyzus korschelti), floury Apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), as well as scale and mealybugs (Coccina) e.g. B. the ivy shield (Aspidiotus hederae) and cup scale (Lecanium hesperidum) and the Lubricant lr.us (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips femoralis and bed bugs, for example the beet (Piesma quadrata), in cotton (Dysdercus intermedius). Bed bug (Cimex lectularius), predatory bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans), also cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars (Lepidoptera) like that should be mentioned in particular Cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar). Goldafter (Euproctis chrysorrhoea) and ringed moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the Saateulc (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frostworm (Cheimatobia brumata). Oak moth (Tortrix viridana), the army worm (Laphygma frugiperda) and Egyptian cotton worms (Prodenia litura), also the web (Hyponomeuta padella). Flour (Ephestia kühniella) and large wax moth (Galleria mellonella).

The biting insects also include beetles (Coleoptera), e.g. B. Corn (Sitophilus granarius = Calandra granaria). Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosusJ. Khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), maize (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common meal (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also those living in the ground Species, e.g. wiry worms bo (Agriotes spec.) And grubs (Melolontha melolontha); cockroaches such as the German (Blattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderac). Oriental (Blatta orientalis), Giant (Blaberus giganteus) and h ^r ) black giant cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; also orthopters. / .. H. the Heimschen (Gryllus domesiieus); Termites such as the terrestrial termites (Reticulitermes flavipcs) and Hymcnoptercn

like ants, for example the meadow ant (l.asius riger).

The Diptera essentially comprise I lie like the dew (Drosophila mclanogastc :) Mittelmcerfruchl · (Ceratitis capilata). Parlor- (Musca domestica), small Parlor (Fannia canicularis), gloss (Phormia regina) and blowfly (Calliphora crythrocephala) as well as the calf stick (Stomoxys calcitrans): also Mükken. z. P. Mosquitoes such as the yellow fever (Aedes aegypti). House mosquito (Culex pipiens) and malaria mosquito (Anopheles stephensi).

The mites (Acari) include especially the spider mites (Tetranychidae) such as the bean (Tetranychus) telarius = Tetranychus althaeae or Tetranychus urticac) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), gall mites, e.g. B. the currant mite (Eriophyes ribis) and tarsonemids for example the shoot tip mite ^ Hemiiarsonemus latus) and cycame mite (Tarsonemus pailidusj; finally ticks like the leather tick (Ornithodorus moubata).

Draw when used against hygiene and storage pests, especially flies and mosquitoes the process products also have an excellent residual effect on wood and clay as well as good alkali stability on limed substrates.

The active compounds according to the invention can be converted into the customary formulations, such as Solutions, emulsions. Suspensions, powders, pastes and granulates. These are done in a well known manner manufactured, e.g. B. by mixing the active ingredients with extenders ^ so liquid solvents, under Liquefied gases under pressure and / or solid carriers, optionally using surface-active agents, i.e. emulsifiers and / or dispersants. In the case of use of water as an extender can be, for. B. also used organic solvents as auxiliary solvents will. The main liquid solvents are: aromatics, such as xylene, toluene, Benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or Paraffins, e.g. B. Petroleum Fractions. Alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, Methyüsobutylketon or cyclohexanone, strongly polar solvents such as Dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant liquids which are stored at normal temperature and under normal pressure are gaseous. z. B. aerosol propellants such as halogenated hydrocarbons, e.g. B. Freon; as fixed Carriers: natural rock flour, such as kaolins,

Table 1
(Myzus test)

Clays, talc, chalk, quartz. Atiapulgii. Monimorrillnnit or Diaii enerde. and synthetic rock flour c. like finely divided silica. Aluminum oxide and silicates: as emulsifiers: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyvinyl alcohols. / .. B. alkylaryl polyglycol ether. Alkyl sulfonates. Alkylsulfaie and Arylsulfonate: as dispersants: / .. B. Lignin. Sulphite liquors and methyl cellulose.

ίο The active ingredients according to the invention can be used in the Formulations are present as a mixture with other known active ingredients.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferred Γι wich between 0.5 and 90%.

The active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates. Emulsions, suspensions, wettable powders. Pastes, soluble powders. Dusts and granules are used. The application happens in usual way, e.g. B. by spraying. Spraying, misting, dusting, scattering, smoking. Gassing, To water. Pickling or encrusting. The active ingredient concentrations in the application-ready Preparations can be varied over a wide range. Generally they lie / wipe 0.0001 and 10%. preferably between 0.01 and 1%.

The active ingredients can also be used with good success in the ultra-low-volume process (LJLV), where possible. To apply formulations up to 95% or even the 100% active ingredient alone.

example 1 Myzus test (contact effect)

Solvent: J parts by weight acetone Emulsifier: 1 part by weight

Alkylaryl polyglycol ethers

To produce an appropriate preparation of active ingredient, I part by weight of active ingredient is mixed with the specified amount of solvent that contains the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

The active compound preparation is used to produce cabbage plants (Brassica oleracea), which are strongly derived from the peach aphid (Myzus persicae) are infested, sprayed dripping wet.

After the specified times, the degree of destruction is determined in%. 100% means that all Aphids were killed, 0% means that none of the aphids were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are based on the following Table I shows:

Active ingredient

Active ingredient concentration
in %

Degree of destruction in% after 1 day

CH ₃ SS

PN = CH-OC ₂ H ₅

/
CH ₃ O (known) (A)

0.1
0.01

100 20

7th 1 Ul ISL-i / lllll ' / CH ₃ O / C ₂ H ₅ O / CH ₃ O / C ₂ H ₅ O / C ₂ H ₅ O CH ₃ O 17 101 8th Ablütijngsgraii penetrates the ground. is the killing means no Effective loll CH ₂ = CH-CH ₂ S 0 CH = C-CH ₂ S 0 CH = C-CH ₂ SO 0 Example 2 (known) (A) in "'ή after 1 day without wetting the leaves of the bean plants. Of the degree determined in%. 100% means that all Ml Ml Ml CH ₃ - NH - C - CH, S 0 WirkslMllVnii / iMilialimi Active ingredient is obtained from the bean plants in the soil
recorded and thus reaches the infected
4 ζ Rlättprn Aphids killed, 0% CH ₁ = CH-CH ₁ S 0 PN = CH-OC ₂ H ₅ PN = CH-OC ₂ H ₅ PN = CH-OC ₂ H ₅ 'Ml Doralis test (systemic effect) in ";. 100 Htl DiaHCI II.
According to the times indicated 3 lice were killed. the following Ml PN = CH-OC ₂ H ₅ Solvent: 3 parts by weight of acetone
Emulsifier: 1 part by weight 100 50 active ingredients, active ingredient concentration tra PN = CH-OC ₂ H, Alkylaryl polyglycol ethers 0.1 95 times and results are running out For the production of an appropriate drug additive 0.01 Table 2 shows: reitung mixing \ part by weight of active substance with the 0.001 specified amount of solvent that the specified 100 Degree of mortality Contains amount of emulsifier and dilutes the concentrate 98 in% after 4 days with water to the desired concentration. 0.1 60 Active ingredient concentration With the active ingredient preparation are bean plants 0.01 in% zen (Vicia faba), which differ greatly from the black 0.001 0 Table 2 100 (Doralis test / systemic effect) 95 0.01 Active ingredient 0.1 80 0.01 CH ₃ SS 0.001 MII 100 PN = CH-OC ₂ H ₅ 99 0.1 95 0.01 0.001 100 100 0.1 50 0.01 0.001 40 bean louse (Doralis fabae) are infested, poured on, so that the active ingredient preparation in 25th

I οι Is

Active ingredient

Act si olTk on ze nl r; il inn

111 "Λ,

Degree of desoldering in "/ '" after 4 days

CH J = CH-CH ₂ S 0
Ml
P - N = CH - OCjH ₅ CH ₃ O CH J = CH-CH ₂ S 0
Wed
Ρ — Ν
/ = CH -OC ₂ H ₅ C ₂ H ₅ O CH = C-CH ₂ S 0
Ml
PN =
/ CH-OCjHs /
CH ₃ O CH = C-CH ₂ S 0
Ml
PN =
/ CH-OC ₂ H ₅ /
C ₂ H ₅ O 0
Μ CH Il
j-NH-C-CH ₂ SO
Ml
P.
/ -N = CH-O /
C ₂ H ₅ O Example 1 3

0.01

100

0.01

100

0.01

100

0.01

100

0.01

100

45

Tetranychus test (resistcnt)

Solvent: 3 parts by weight of acetone. Emulsifier: 1 part by weight

Alkylaryl polyglycol ethers

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent that contains the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

With the active ingredient preparation, bean plants are

Table 3
(Tetranychus test / resistant)

zen (Phaseolus vulgaris), which have a height of about 10-30 cm, sprayed until dripping wet. These bean plants are heavily infested with all stages of development of the common spider mite (Tetranychus urticae).

After the times given, the effectiveness of the active compound preparation is determined by the counts dead animals. The degree of destruction obtained in this way is given in%. 100% means all Spider mites have been killed, 0% means that no spider mites have been killed.

Active ingredients, active ingredient concentrations. Evaluation times and results are based on the following Table 3 shows:

Active ingredient

Ingredient concentration
in %

Degree of destruction in% after 2 days

CH ₃ SS

MII

PN = CH-OC ₃ H ₅

/
CH ₃ O

(known) (A)

0.01

11 12

Active ingredient Wi rkstollVoive nt ration Removal grip

in% in% after 2 layers

CH ₂ = CH-CH ₂ SO

P-N = CIl-OQH, 0.1 98

CH ₃ O
CH ₂ = CH-CH ₂ SO

PN = CH-OC ₂ H ₅ 0.1 99

C ₂ H ₅ O
CH = C-CH ₂ S 0

^X p_N = CH-OC ₂ H ₅ 0.1 98

CH ₃ O
CH = C-CH ₂ S 0

PN = CH-OC ₂ H ₅ 0.1 98

C ₂ H ₅ O

B e i s ρ i e I 4 9.5 cm. The Petri dish remains open until

the solvent has completely evaporated. | e after LDioo-Test concentration of the active ingredient solution is the amount

Test animals: Sitophilus granarius ^ ¹ * !! ^ ^P J ° f ^Filler P ^a P ^{ier of} different heights.

Solvent-acetone ³⁵ Then about 25 test animals are placed in the

⁶ 'Petri dish and cover it with a glass lid.

2 parts by weight of active ingredient are in 1000 parts by volume. The condition of the test animals is 3 days after preparation

len solvent added. The tests obtained in this way are checked. The killing is determined

Solution is adjusted to the in% with further solvent.

desired concentrations. 40 active ingredients, active ingredient concentrations, test animals and

2.5 ml of active ingredient solution are placed in a Petri dish. The results are shown in Table 4 below

pipetted. On the bottom of the Petri dish you can find:
a filter paper with a diameter of about

Table 4
(LD ₁₀₀ test / Sitophilus granarius)

Active ingredient Active ingredient concentration Degree of destruction

of the solution in% in%

Il

(CH ₃ O) ₂ PS-CH ₂ -CH ₂ -SO-C ₂ H ₅ 0.2 20

(known)

CH ₂ = CH-CH ₂ -SO

PN = CH-OC ₂ H ₅ 0.2 100

CH ₃ O
CH ₂ = CH-CH ₂ SO

PN = CH-OC ₂ H ₅ 0.2 100

C ₂ H ₅ O

rurixci / Ulli ' C-CH ₂ -S 13th / 2 B 17 101 14th ΛΜοΙιιημ-, μκκΙ
in "■■" Effective loll CH ₃ O ₂ SUN
Mil
PN = CH- \ V! RkNtiillV <Hi, "'ntr; ii u in
the solution in ". '.. 100
100 CH = C-CH ₂ -S O
Ml
PN = CH-OC 2H ₅ 0.2
0.02 C ₂ H ₅ O 100
100 CH = -CH ₂ -CH O
PN = CH-OC 2H ₅ 0.2
0.02 100
70 C ₂ H ₅ S -OC ₂ H 5 0.2
0.02

C ₂ H ₅ O

Example

LTnKi test for dipteras

Tcs.uere: Musca domesuca

Solvent: acetone

2 parts by weight of active ingredient are in 1000 parts by volume Solvent added. The solution obtained in this way is added to the desired lower concentrations. »

2.5 ml of the active ingredient solution are piped into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains open until the solution mill! has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m ^{2 of} filter paper varies. Then about 25 test animals are placed in the Petri dish and covered with a glass lid.

The condition of the test animals is continuously monitored. The time is determined which for a IOO% knock down effect is necessary.

Test animals, active ingredients, active ingredient concentrations and times at which a 100% knock down effect is available, can be seen from the following table 5:

Table 5

(LTi ₀₀ -Test for Diptera / Musca domestica)

Active ingredient

Active ingredient concentration LTjoo in

of the solution in% minutes (') or

Hours (h)

Il

(CH ₃ O) ₂ PS-CH ₂ -CH ₂ -SO-C ₂ H ₅

(known)

CH ₂ = CH - CH ₂ -SO

Ml

PN = CH-OC ₂ H ₅ CH ₃ O
CH ₂ = CH-CH ₂ -SO

MII

PN = CH-OC ₂ H ₅ C ₂ H ₅ O

0.2

0.2
0.02

0.2
0.02

195 '

25 '
110 '

100 '
Oh

15th

I'orisci / uim

Active ingredient

Active substance concentration LTmo in

of the solution in% minutes (') or

Hours (h)

= C-CH ₂ -S

\ ll

PN = CH-OC ₂ H ₅ CH ₃ O

= C-CH ₂ -S

Ml

PN = CH-OC ₂ H ₅ C ₂ H ₅ O CH ₃ -NH-CO -CH ₂ -S

Ml

PN = CH-OC ₂ H ₅ C ₂ H ₅ O 0.2
0.02

0.2
0.02

0.2
0.02

20 '100'

25 '6h

100 '6h

Preparation examples Example 6

CH ₂ = CH-CH ₂ S

Mil

PN = CH-OC ₂ H ₅ C ₂ H ₅ O

A mixture of 36 g (0.2 mol) of O-ethyl-S-allylthiol-aUylthiolphosphoryl / I-iminoformic acid ethyl ester with phosphoric acid diesteramide. 30 g of orthoformic acid with a boiling point of 96 ° C / 0.01 Torr and the refractive ethyl ester and 1 g of p-toluenesulfonic acid is 30 minutes w dex n ": 1.4962.

Boiled at 100 ° C (10 cm Vigreux column), then the following compounds can be prepared analogously

Bend the reaction mixture distilled. One obtains the following: 35 g (77% of theory) of the desired N- (O-ethyl-S-

constitution

Physical data
[Boiling point ( ⁰ C);
Refractive index]

yield

(% of theory)

CH = C-CH ₂ SO

MII

PN = CH-OC ₂ H ₅

/ C ₂ H ₅ O

CH ₂ = CH-CH ₂ S

MII

PN = CH-OC ₂ H ₅

/ CH ₃ O

CH = C-CH ₂ SO

Ml

PN = CH-OC ₂ H ₅ CH ₃ O 102 / 0.01 Torr n ^! _D ^! : 1.5049

96 / 0.01 Torr n'J: 1.5011

102 / 0.01 torr
njj ': 1.5118

68

81

63

230 242/225

constitution

Physical data
! Boiling point ( ⁰ C);
Refractive index]

yield

(7o of theory)

CH ₃ -NH-CO-CH ₂ S 0

PN = CH-OC ₂ H ₅ C ₂ H ₅ O
C ₂ H ₅ S-CH ₂ -CH ₂ -SO

PN = CH-OC ₂ H ₅ C ₂ H ₅ O
C Hj = CH - C H2S S

PN = CH-OC ₂ H ₅ CH ₃ O
CH ₂ = CH-CH ₂ SS

PN = CH-OC ₂ H ₅ C ₂ H ₅ O
C ₂ H ₅ S-CH ₂ -CH ₂ -SS

PN = CH-OC ₂ H ₅ CH ₃ O
C ₂ H ₅ S-CH ₂ -CH ₂ SS

PN = CH-OC ₂ H ₅ C ₂ H ₅ O

n £, ': 1.5032

39

118 / 0.01 torr

74

The following compounds can also be established will:

O-ethyl-S-iN-monomethylcarbamoylmethyl) -.

O-n-Propyl-S- (N-monomethylcarbamoylmethyl) -,

O-iso-propyl-S-

(N-monomethylcarbamoy! Methyl) -. O-butyl-S- (N-monomethylcarbamoylmeihyl) -, O-methyl-S-iN-monoäthylcarbamoylmethyl) -, O-ethyl-S- (N-monoethylearbamoylmethyl) -. O-butyl-S- (N-monoäthylcarbamoylmethyl) -, O-methyl-S-methylmercaptoethyl-, O-iso-propyl-S-methylmercaptoethyl, O-ethyl-S-äthylmercaptoäthyl- and O-sec-butyl-S-ethylmercaptoethylthiolphosphoryliminoformic acid

ethyl ester,
other alkyl esters and their thiono analogs.

The required starting compounds (II) can, for. B. can be produced as follows:

C ₂ H ₅ -S-CH ₂ -CH ₂ SO

C ₂ H ₅ O

P-NH ₂ Ola)

63 g of 2-chloroethylethylthioether are added to 105 g (0.5 mol) of the sodium salt of O-ethylihiolphosphoric acid cesieramide in 250 ml of methanol. The reaction mixture is ^{stirred at 70 °} C. for 1 hour, after cooling it is poured into 200 ml of water and extracted 3 × with 200 ml of chloroform each time. After the organic phase has dried, the solvent is distilled off and the residue is distilled off. 106 g (93% of theory) of O-ethyl-S-ethylmercapioäthylthiolphosphorsäurediesteramid with a refractive index n °: 1.5334 are obtained. The oil obtained crystallizes and, on recrystallization from a mixture of ethyl acetate and ligroin, a product which melts at 50 ° -53 ° C. is obtained.

The following compounds can be obtained in an analogous manner:

I ^l9

SS constitution physical data

ps (melting point [ ⁰ C];

#; Refractive index)

(P

κί "

ψ. CH ₂ = CH-CH ₂ SO

| I Ml

If P-NH ₂

IC ₂ H ₅ O

CH ^ C - CH ₂ SO

P-NH ₂

C ₂ H ₅ O

(lic)
CH ₂ = CH-CH ₂ SO

\ ll

P-NH ₂

CH ₃ O

(Hd)

CH ^ C-CHjS O

\ ll

P-NH ₂ ji ": 1.5296

/ CH ₃ O

the)
CH ₃ -NH-CO-CH ₂ S

\ ll

P-NH ₂

C ₂ H ₅ O

Claims (1)

Patent claims: I. N- [O-alkyl-S-a! Iphatischc (lhiünij) -thiolphos phoryl] -iminoformic acid alkylsier of the formula R'S X P-N = CH-OAIk (D in which R alkyl around! to b, R ' alkenyl or alkynyl with 2 to b, lower alkyliriercaptoalkyl or N-alkylcarbamoylnic- thyl. means while
Alk represents alkyl having 1 to 6 carbon atoms and a
X is an oxygen or sulfur atom,